We have successfully developed a novel electrolytic system using solid-supported bases for in situ generation of a supporting electrolyte from methanol as a solvent. Anodic methoxylation of phenyl 2,2,2-trifluoroethyl sulfide using solid-supported bases was carried out to provide the α-methoxylated product in good to excellent yields. The α-methoxylated product and solid-supported bases were easily separated by only filtration, and the separated solid-supported bases were recyclable. Anodic methoxylation of phenyl 2,2,2-trifluoroethyl sulfide was successfully carried out 10 times by the recycling of silica gel-supported piperidine in good yields.